|Publication number||US5059417 A|
|Application number||US 07/544,306|
|Publication date||Oct 22, 1991|
|Filing date||Jun 26, 1990|
|Priority date||Jun 26, 1990|
|Also published as||CA2045266A1, CA2045266C, DE69101089D1, DE69101089T2, EP0464913A1, EP0464913B1|
|Publication number||07544306, 544306, US 5059417 A, US 5059417A, US-A-5059417, US5059417 A, US5059417A|
|Inventors||David R. Williams, Christine W. Ryles|
|Original Assignee||Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (18), Non-Patent Citations (2), Referenced by (102), Classifications (20), Legal Events (7)|
|External Links: USPTO, USPTO Assignment, Espacenet|
1. Field of the Invention
The invention relates to a gel dentifrice containing peroxide and a viscosity stabilization system.
2. The Related Art
Aqueous hydrogen peroxide is widely viewed by the dental profession as an effective treatment against gum disease. Periodontal disorders are believed to arise from infectious anaerobic microorganisms which are active in the absence of oxygen. These microorganisms can be controlled or entirely eliminated by contact with peroxides which release oxygen. According to this rationale, oxygen creates an aerobic atmosphere destructive to the microorganisms.
Facile reactivity of the peroxide benefits performance but conversely results in storage stability problems. Dentifrices containing peroxides tend to decompose within a relatively short period of time. Not only is activity lost but there can be a marked breakdown in the dentifrice's physical properties. Dentrifice viscosity is particularly adversely affected by the chemical breakdown of thickening agents. A variety of techniques have been developed to counter the problem. U.S. Pat. No. 4,226,851 (Sompayrac) discloses oral compositions comprising hydrogen peroxide and zinc chloride wherein vitamin E is added as a stabilizing agent. U.S. Pat. No. 4,788,052 and U.S. Pat. No. 4,839,157 both to Ng et al. report stable aqueous hydrogen peroxide gel dentifrices stabilized with a combination of hydrophilic and hydrophobic fumed silica. These gels include polyethylene glycol, sodium saccharin, sodium benzoate, polyethylene oxide type nonionic surfactant and flavor all maintained at a pH of 3-6, preferably 4.5-5, through acidification with phosphoric or citric acids. A related patent, U.S. Pat. No. 4,839,156 (Ng et al), further specifies use of polyoxyethylene-polyoxypropylene block copolymers, polyethylene glycol, nonionic surfactant and flavour. Again citric or phosphoric acids maintain a pH of about 4.5 to 6.
Stability may also be enhanced by employing relatively non-reactive components. For instance, U.S. Pat. No. 4,684,517, U.S. Pat. No. 4,537,778 and U.S. Pat. No. 4,431,631 all to Clipper et al report wintergreen and cinnamon flavors as being non-reactive in peroxide oral preparations. Other components include 1-20% polyhydric alcohols such as glycerol and up to 3% of polyoxyethylene-polyoxypropylene nonionic surfactants. Other patents such as U.S. Pat. No. 4,302,441 (Muhlemann et al) recommend that solid oral preparations comprising urea hydrogen peroxide be formulated without glycerol so as to be more effective against microorganisms on teeth. Glycerol was said to inhibit saliva and components thereof from beneficially decomposing the peroxide.
Oral compositions containing both a peroxide and sodium bicarbonate have been acclaimed by the dental profession, especially through the work of Keyes. See Keyes et al "Periodontics and Oral Hygiene", Jan. 1978, pages 51-56. Unfortunately, formulations based on the Keyes technology are particularly prone to decomposition. Several approaches have been reported to overcome difficulties presented by such combination of ingredients. U.S. Pat. No. 3,577,521 (Scheller) discloses use of acid salts in combination with alcohol-silica gels to obtain a foaming storage-stable toothpaste of peroxide-bicarbonate. U.S. Pat. No. 4,837,008 (Rudy et al) overcomes the problem through a non-aqueous dentifrice wherein an inorganic peroxide and/or bicarbonate is coated with a water-soluble barrier which is insoluble in the dentifrice vehicle.
U.S. Pat. No. 4,130,501 (Lutz) describes stable viscous hydrogen peroxide solutions formulated with Carbopol® thickener, a polyoxyethylene-polyoxypropylene surfactant and a neutralizing agent to raise pH between 4.5 and 8.
A physical separation into separate compartments of the peroxide from co-reactive ingredients has been another approach to the problem. U.S. Pat. No. 4,849,213 and U.S. Pat. No. 4,528,180 both to Schaeffer disclose a dual-compartment package with gel and paste components, respectively. The gel component includes hydrogen peroxide, a Carbopol® type thickener, a nonionic cellulose and a basic neutralizing agent with pH maintained at about 3-6.
U.S. Pat. No. 4,895,721 (Drucker) has focused both on the problem of viscosity and peroxide loss. Prevention of these problems is achieved through a gel base of 35-95% polyol (e.g. glycerol), and 0.75-5% gelling agent (e.g. Carbopol®), and 0.05-1% antioxidant or U.V. absorber with pH maintained at 3.5-6.5.
U.S. Pat. No. 4,343,785 (Schmolka) discloses a gel dentifrice containing a cogeneric mixture of polyoxybutylene-polyoxyethylene block copolymers (Pluronic® type) which may contain glycerol and be pH adjusted with citric acid. The combination is reported as retarding plaque formation and growth. The gel structure is retained even below 20° C.
From all of the aforementioned art, it is apparent that hydrogen peroxide compositions should be formulated as simply as possible to minimize potential interactions between the peroxide and the remaining ingredients. Notwithstanding such precautions, gels can lose viscosity turning into the fluid state as temperature decreases. Except for U.S. Pat. No. 4,343,785, the literature has not appreciated that dental gels based on Pluronic® type formulations suffer from low temperature gel structure loss. This situation is rendered more difficult when a peroxide is formulated with the product. Even further difficulties arise where the peroxide gel is packaged within an expandable pump dispenser. At temperatures below 10° C., gel consistency is lost, the product turns liquid and then leaks out of the dispenser.
Accordingly, it is an object of the present invention to provide a peroxide containing gel composition that maintains structure even at temperatures below 10° C.
A further objective of the present invention is to provide a peroxide containing gel composition which under low temperature conditions remains confined to a pump dispenser package.
Another object of the present invention is to provide a gel composition of exceptional clarity.
A still further objective of the present invention is to achieve all of the above in combination with retaining a high peroxide stability.
These and other objects of the present invention will become more readily apparent upon consideration of the more detailed description and Examples which follow.
An oral composition is provided comprising:
(i) about 0.1 to about 10% by weight of a peroxygen compound;
(ii) from more than 30% to less than 50% by weight of glycerol; and
(iii) a polyoxyethylene-polyoxypropylene copolymer in an amount so that a weight ratio of glycerol to copolymer ranges from 1:0.7 to 1:0.4, and the composition has a cohesion value ranging from 100 to 360 g.
Advantageously, the oral composition will contain hydrogen peroxide as the peroxygen compound and be present in a form of a clear gel composition. Best results may be obtained when pH of the composition is held to less than 3.0.
Now it has been found that there are several critical conditions required to achieve a chemically stable peroxide formulated gel produced of good low temperature physical stability. Present in the composition must be a combination of water glycerol (sometimes termed glycerin), and a polyoxyethylene-polyoxypropylene copolymer. Advantageously present may also be a phosphorus containing mineral or organic acid. Relative concentration of these components has been found to be quite critical and lying within a very narrow range.
The above noted components were chosen because they met the minimum functional requirements of the gel phase. These components also maximize the hydrogen bonding potential of the aqueous medium, thereby being a significant factor in the stabilization of hydrogen peroxide. Formulations of this invention exhibit very high stability; preparations held at elevated temperatures (105° F.) for nine months still had well in excess of 90% of the peroxide originally added.
The polyoxyethylene-polyoxypropylene copolymers of this invention are most suitable where the hydrophobic portion, represented by (C3 H6 O), has a molecular weight ranging from about 2,750 to 4,000 and the hydrophilic portion, represented by (C2 H4 O), constitutes about 70-80% of the weight of the copolymer. Commercially the copolymers are available from the BASF Corporation under the trademark, Pluronic F88, F99, F108 and F127. Most preferred is Pluronic F127 (hereinafter referred to by its CTFA name, Poloxamer 407) which has a molecular weight ranging from about 10,000 to 15,000, and containing about 70% of the hydrophilic polyoxyethylene moiety. Amounts of the copolymer can range anywhere from 18-25% by weight, preferably between 19 and 24%. Poloxamers are particularly suitable for this invention because of their wide pH tolerance, high compatibility with hydrogen peroxide and unique gel properties.
Below 45° F. the Poloxamer copolymers, however, do not form a gel structure in water, probably due to the reduced solubility of the hydrophobic portion. Indeed, manufacturers of the copolymer report in their literature that general formulations are best prepared below 45° F., where the water-like viscosity liquid phase is easy to process, package and fill. As the temperature rises above 45° F., the thermo-reversible gel forms in the pack. Gel transition occurs rapidly, in a matter of minutes, and normally does not adversely effect the product as both liquid and gel phases are completely homogeneous and stable. Nevertheless, there are many concerns with the loss of viscosity at low temperatures. For instance, the gel/liquid transition during winter months might be crossed many times before the end use of the product. Furthermore, as often happens with dentrifice products, they may be left overnight next to a bathroom window, exposing them to temperatures below 45° F. Finally, in situations where the package designed for this product is based upon a toothpaste pump, the piston seals may not retain the low viscosity liquid phase.
Based on the above considerations, it is important to formulate a gel that avoids low temperature liquification, while still maintaining good storage stability.
A combination of Poloxamer and glycerol, in special ratio, has been found which accomplishes both purposes. The Poloxamer component stabilizes the peroxide while the glycerol inhibits liquification of the Poloxamer at the low temperature.
The glycerol must be present in an amount greater than 30% and less than 50%, preferably from about 35% to 45%, optimally about 40% by weight.
Critical for the invention is that the weight ratio of glycerol to the polyoxyethylene-polyoxypropylene copolymers be within the narrow range from 1:0.7 to 1:0.4, preferably between 1:0.6 and 1:0.45, optimally about 1:0.5.
Advantageously, the compositions of this invention will be maintained at a low pH, preferably a pH of less than 3, optimally being of pH no higher than 2.8. While there is no set lower end of the pH range, for practical reasons pH of the composition will not be less than about 0.0 and usually not less than 2.0. Acidification is best accomplished through use of a phosphorous-based inorganic or organic acid. Most effective is phosphoric acid.
Water will be present in the compositions in amounts ranging from about 35% to about 55%, preferably between about 40% to 50% by weight.
A variety of water-soluble peroxygen compounds, such as sodium perborate, persilicate, perphosphate and hydrogen peroxide, may be employed. The most suitable for this invention is hydrogen peroxide itself. The amount of the peroxygen compound may range from about 0.1 to about 10% by weight. In terms of active weight hydrogen peroxide, the amount will range from about 0.5% to about 3%, preferably from about 0.8% to about 1.8%, optimally between about 1% and 1.5% by weight.
Adjunct minor ingredients may also be present in the composition of this invention. Included may be small amounts of colorant, and antioxidant. Thickeners, such as cross-linked polyacrylates, e.g. Carbopol R, flavors and cellulosic or other gums will normally be absent to avoid interaction with the peroxide.
The following examples will more fully illustrate the embodiments of this invention. All parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise illustrated.
This example reports evidence of the glycerol: Poloxamer ratio and Poloxamer level necessary to achieve viscosity retention at low temperatures. A series of formulations were prepared incorporating 4.285% hydrogen peroxide (35% active, food grade), 1% phosphoric acid (12.75% active wt/wt), and variable levels of deionized water, Poloxamer 407 and glycerol. These components were blended together forming a 1.5% hydrogen peroxide clear gel.
Tables I-III set forth the effects of varying the ratio of glycerol to Poloxamer 407 as relates to gelation temperature.
TABLE I______________________________________Effect of Glycerol at Constant (25%) Poloxamer 407______________________________________Poloxamer 407% 25 25 25 25Glycerol % 10 20 25 50G:P Ratio 1:2.5 1:1.25 1:1 2:1Gellation Temp. F. 51 32 9 No gelViscosity (cohesion g) 250 >360 >360 --______________________________________
TABLE II__________________________________________________________________________Effect of Glycerol at Constant (20%) Poloxamer 407__________________________________________________________________________Poloxamer 407% 20 20 20 20 20 20 20 20Glycerol % 10 20 30 35 40 42.5 45 50G:P Ratio 1:2 1:1 1:0.67 1:0.57 1:0.5 1:0.47 1:0.44 1:0.4Gellation Temp. F. 65 45 21 11 5 0 -1 55Viscosity (cohesion g) 55 175 230 240 230 280 280 95__________________________________________________________________________
TABLE III__________________________________________________________________________Effect of Poloxamer at Constant Glycerol (20%) (40%) (50%)__________________________________________________________________________Poloxamer 407% 20 25 27.5 30 32.5 17.5 20 15 20 25Glycerol % 20 20 20 20 20 40 40 50 50 50G:P Ratio 1:1 1:1.25 1:1.38 1:1.5 1:1.63 1:0.44 1:0.5 1:0.3 1:0.4 1:0Gellation Temp. F. 45 32 23 15 <3 20 5 No gel* 55 No gel*Viscosity 175 335 >360 >360 >360 <100 230 <100 95 <100(cohesion g)__________________________________________________________________________ *Much greater than 70° F.
From Table I it can be seen that increasing the glycerol level advantageously lowers the temperature of gelation. However, there were two problems. The gels formed were extremely "hard" as indicated by the high viscosities (measured as the force in grams required to pull apart two plates sandwiching a uniform thickness of the gel). In fact, the gels were too hard to be processable by conventional toothpaste industry means. The upper range is usually set at 250 g, although processability is probably possible up to 300 g. Secondly, the gels could not be prepared at high glycerol concentrations; an attempt to make a gel with a Glycerol:Poloxamer (G:P) ratio of 2:1 (at 25% Poloxamer) was unsuccessful. The Poloxamer would not completely hydrate in 50% glycerol.
The aforementioned experiments were repeated at 20% Poloxamer where a similar trend was followed. See Table II. These results clearly demonstrated that gelation temperatures can be lowered by increasing glycerol content of the gel. The gels formed were softer and fell within the processable range. The G:P ratio of 1:0.5 (at 20% Poloxamer) was identified as the optimum. At this level the gel had low enough gelation temperature (5° F.) to minimize liquification problems and allow a formulation safety margin below the higher (45-50%) glycerol levels where the trend failed and gelation temperatures rose again. There was an added benefit in the 1:0.5 (G:P) ratio formulation in that the liquid phase below 0°-3° F. had a quite high "honey-like" viscosity which also did not leak from a pump package.
In order to assess whether another optimum low gelation temperature could be achieved at other Poloxamer loadings, the experiment was repeated at 20, 40 and 50% glycerol. Table III reports the gelation temperature as a function of Poloxamer level for these three levels of glycerol. The results indicate that at lower (20%) glycerol levels, low gelation temperatures can be achieved. However, to achieve gelation temperatures down below 10° F., the Poloxamer level needed to be raised to 35% where the gels produced were far too "hard" (cohesions well in excess of 360 g) to be readily processed. At 40% glycerol, there was a similar trend. Attempts to prepare gels at 50% glycerol were not very successful. The data suggests that there was too little water to hydrate the Poloxamer (@25%) and too little Poloxamer (@15%) to form stable gels. This is similar to the trend in Table II where, in the 45-50% glycerol range, the nature of the formulation changes and gelation temperature is no longer reduced by increasing glycerol.
Based upon the foregoing experiments, it is concluded that Poloxamer gels formulated at a G:P of about 1:0.5 (20% Poloxamer loading), exhibit good low temperature gel stability and can be readily processed.
Table IV demonstrates how the pH of the gel, adjusted by phosphoric acid content, has effects upon peroxide stability. The pH needed to be maintained below 3.0, especially at 2.8 or less to maximize stability. Nominal pH of the formula evaluated under Table II was 2.5. Hydrochloric acid completely destabilized the peroxide gel. Neither nitric nor citric acids met the >80% stability criteria, although the stability of these gels were better than that containing hydrochloric acid.
TABLE IV______________________________________Effect of Gel pH on Hydrogen Peroxide Stability(Phosphoric Acid)pH PSST Stability %______________________________________6.35 295.9 365.7 314.25 374.1 363.84 323.6 363.48 393.29 323.03 592.72 100______________________________________
Hydrogen peroxide: The majority of the hydrogen peroxide studies were undertaken as accelerated storage studies at 105° F. The criteria for stable product required >80% of the peroxide remaining after three months. The peroxide level was measured in the standard way by oxidizing potassium iodide to iodine and titrating with sodium thiosulphate on an auto-titrator fitted with a redox electrode.
In order to speed up the information feedback loop on peroxide stability a high temperature (203° F.) short time (6 hours) test was developed which demonstrated good correlation with the 105° F. storage. This fast test has been called the Peroxide Stability/Stress Test (PSST). The peroxide content of the gel was assayed as described above, and assessed against the same criteria.
Gelation Temperature: This was measured by cooling down the gel well into the liquid phase state. The liquid was then allowed to warm slowly at room temperature until the gel began to reform. The temperature taken at this point was the gelation temperature.
The foregoing description and examples illustrated selected embodiments of the present invention. In light thereof, various modifications will be suggested to one skilled in the art, all of which are within the spirit and purview of this invention.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3577521 *||Jul 14, 1967||May 4, 1971||Scheller Durodont Dr||Storage-stable frothing toothpaste|
|US3639574 *||Oct 25, 1967||Feb 1, 1972||Basf Wyandotte Corp||Stable hydrogen peroxide gels|
|US4130501 *||Sep 20, 1976||Dec 19, 1978||Fmc Corporation||Stable viscous hydrogen peroxide solutions containing a surfactant and a method of preparing the same|
|US4226851 *||Jul 11, 1979||Oct 7, 1980||Sompayrac Hewitt A||Stable dental composition containing hydrogen peroxide|
|US4302441 *||Apr 11, 1980||Nov 24, 1981||Hans R. Muhlemann||Solid oral preparations of urea hydrogen peroxide without glycerol|
|US4343785 *||Aug 10, 1981||Aug 10, 1982||Basf Wyandotte Corporation||Gel dentifrice compositions|
|US4431631 *||Jan 3, 1983||Feb 14, 1984||Colgate-Palmolive Company||Aqueous oral solution|
|US4465663 *||Jul 27, 1981||Aug 14, 1984||Basf Wyandotte Corporation||Polyoxybutylene-polyoxyethylene aqueous gels|
|US4528180 *||Mar 1, 1983||Jul 9, 1985||Schaeffer Hans A||Dental preparation, article and method for storage and delivery thereof|
|US4537778 *||Feb 13, 1984||Aug 27, 1985||Colgate-Palmolive Company||Oral preparation|
|US4684517 *||Sep 30, 1986||Aug 4, 1987||Colgate-Palmolive Company||Mouthrinse composition containing hydrogen peroxide and fluoride|
|US4696757 *||Jun 16, 1986||Sep 29, 1987||American Home Products Corporation||Stable hydrogen peroxide gels|
|US4788052 *||Apr 17, 1987||Nov 29, 1988||Colgate-Palmolive Company||Stable hydrogen peroxide dental gel containing fumed silicas|
|US4837008 *||Jan 12, 1987||Jun 6, 1989||Peroxydent Group||Periodontal composition and method|
|US4839156 *||Apr 17, 1987||Jun 13, 1989||Colgate-Palmolive Company||Stable hydrogen peroxide dental gel|
|US4839157 *||Sep 12, 1988||Jun 13, 1989||Colgate-Palmolive Company||Stable hydrogen peroxide dental gel containing fumed silicas|
|US4849213 *||Jun 19, 1987||Jul 18, 1989||Schaeffer Hans A||Dental preparation, article and method for storage and delivery therof|
|US4895721 *||Jan 22, 1988||Jan 23, 1990||Carter-Wallace Inc.||Peroxide gel dentifrice compositions|
|1||*||Periodontics and Oral Higiene, Keyes et al, Jan. 1978, pp. 51 56.|
|2||Periodontics and Oral Higiene, Keyes et al, Jan. 1978, pp. 51-56.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5186926 *||Jan 3, 1992||Feb 16, 1993||Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.||Flavor for peroxide-bicarbonate oral compositions|
|US5217710 *||Mar 5, 1992||Jun 8, 1993||Chesebrough-Pond's Usa Co.||Stabilized peroxide gels containing fluoride|
|US5372802 *||Sep 2, 1993||Dec 13, 1994||Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.||Stabilized peroxide gels containing fluoride|
|US5376006 *||Sep 24, 1992||Dec 27, 1994||Ultradent Products, Inc.||Dental bleaching compositions and methods for bleaching teeth surfaces|
|US5616313 *||Apr 11, 1995||Apr 1, 1997||Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.||Method for treating gingival and periodontal tissues|
|US5632972 *||Jun 30, 1994||May 27, 1997||Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.||Method for treating gingival and periodontal tissues|
|US5658595 *||Sep 10, 1992||Aug 19, 1997||Kon-Des Milieutechnologie B.V.||Method, composition and device for the treatment of raw materials, products and production means, in particular in the foodstuffs industry|
|US5665332 *||Mar 28, 1994||Sep 9, 1997||Oralcare Systems, Inc.||System for delivering foams containing medicaments|
|US5766704 *||Mar 13, 1996||Jun 16, 1998||Acushnet Company||Conforming shoe construction and gel compositions therefor|
|US5778886 *||Feb 27, 1996||Jul 14, 1998||Shihata; Alfred||Vaginal compositions combining a spermicidal agent and a peroxygen compound|
|US5846570 *||Jun 27, 1997||Dec 8, 1998||Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.||Stabilized hydrogen peroxide gel compositions|
|US5851514 *||Aug 2, 1996||Dec 22, 1998||Colgate Palmolive Company||Stable aqueous abrasive peroxide tooth whitening dentifrice|
|US5858332 *||Jan 10, 1997||Jan 12, 1999||Ultradent Products, Inc.||Dental bleaching compositions with high concentrations of hydrogen peroxide|
|US5876995||Nov 25, 1996||Mar 2, 1999||Bryan; Bruce||Bioluminescent novelty items|
|US5881920 *||May 6, 1997||Mar 16, 1999||The Plastek Group||Product dispenser having separable refill cartridge|
|US5881921 *||Jul 31, 1997||Mar 16, 1999||The Plastek Group||Product dispenser having separable refill top loading cartridge|
|US5885556 *||Aug 6, 1996||Mar 23, 1999||The Procter & Gamble Company||Tartar control oral compositions|
|US5888483 *||Oct 21, 1997||Mar 30, 1999||Avon Products, Inc.||Nail bleach|
|US5922307 *||Sep 25, 1996||Jul 13, 1999||R. Eric Montgomery||Tooth bleaching compositions|
|US5928628 *||Oct 23, 1997||Jul 27, 1999||Pellico; Michael A.||Two-component dental bleaching system and method|
|US5935557 *||Feb 12, 1997||Aug 10, 1999||Avon Products, Inc.||Nail bleach|
|US5939157 *||Oct 30, 1995||Aug 17, 1999||Acushnet Company||Conforming shoe construction using gels and method of making the same|
|US5955159 *||Oct 27, 1995||Sep 21, 1999||Acushnet Company||Conforming shoe construction using gels and method of making the same|
|US5958461 *||Jun 20, 1997||Sep 28, 1999||Marshall University Research Corporation||Vaginal pharmaceutical compositions|
|US5985249||Oct 14, 1997||Nov 16, 1999||Ultradent Products, Inc.||Sticky dental compositions for adhering a passive-type dental tray over a person's teeth|
|US5985383 *||Mar 14, 1996||Nov 16, 1999||Acushnet Company||Conforming shoe construction and gel compositions therefor|
|US6036943||Oct 14, 1997||Mar 14, 2000||Ultradent Products, Inc.||Methods for treating a person's teeth using sticky dental compositions in combination with passive-type dental trays|
|US6113886||Nov 22, 1999||Sep 5, 2000||Bruce Bryan||Bioluminescent novelty items|
|US6120754 *||Dec 21, 1998||Sep 19, 2000||Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.||Remineralization of teeth|
|US6152358||Aug 17, 1998||Nov 28, 2000||Bruce Bryan||Bioluminescent novelty items|
|US6214321||Mar 29, 2000||Apr 10, 2001||Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.||Remineralization of teeth|
|US6247995||Feb 6, 1996||Jun 19, 2001||Bruce Bryan||Bioluminescent novelty items|
|US6312666||Nov 12, 1998||Nov 6, 2001||3M Innovative Properties Company||Methods of whitening teeth|
|US6312667 *||Nov 12, 1998||Nov 6, 2001||3M Innovative Properties Company||Methods of etching hard tissue in the oral environment|
|US6322773 *||Aug 13, 1999||Nov 27, 2001||R. Eric Montgomery||Tooth-bleaching compositions|
|US6331292||Nov 16, 1998||Dec 18, 2001||R. Eric Montgomeory||Tooth bleaching compositions|
|US6335001||Dec 27, 1999||Jan 1, 2002||Basf Corporation||Carrier blends for dentifrices comprising ethoxlated polyhydric alcohols|
|US6342206||Dec 27, 1999||Jan 29, 2002||Sridhar Gopalkrishnan||Aqueous gels comprising ethoxylated polyhydric alcohols|
|US6346279||Jul 19, 1999||Feb 12, 2002||Virox Technologies, Inc.||Hydrogen peroxide disinfectant with increased activity|
|US6416960||Aug 8, 1997||Jul 9, 2002||Prolume, Ltd.||Detection and visualization of neoplastic tissues and other tissues|
|US6458547||Dec 12, 1997||Oct 1, 2002||Prolume, Ltd.||Apparatus and method for detecting and identifying infectious agents|
|US6488914||Oct 31, 2001||Dec 3, 2002||R. Eric Montgomery||Tooth bleaching compositions|
|US6514543||Oct 31, 2001||Feb 4, 2003||R. Eric Montgomery||Tooth bleaching compositions|
|US6534043||May 11, 2001||Mar 18, 2003||Unilever Home & Personal Care Usa, Division Of Conopco, Inc.||Stable peroxide dental compositions|
|US6536628 *||Oct 31, 2001||Mar 25, 2003||R. Eric Montgomery||Tooth-bleaching compositions|
|US6551579||May 29, 2001||Apr 22, 2003||The Procter & Gamble Company||Delivery systems for a tooth whitener|
|US6582708||Jun 28, 2000||Jun 24, 2003||The Procter & Gamble Company||Tooth whitening substance|
|US6596257||Dec 22, 2000||Jul 22, 2003||Prolume, Ltd.||Detection and visualization of neoplastic tissues and other tissues|
|US6620405||Nov 1, 2001||Sep 16, 2003||3M Innovative Properties Company||Delivery of hydrogel compositions as a fine mist|
|US6632397||Sep 30, 1999||Oct 14, 2003||Minntech Corporation||Multi-part anti-microbial concentrate system, activated solution, use-dilution solution, method of making same, and method of sterilizing with the use-dilution solution|
|US6649356||Apr 19, 2002||Nov 18, 2003||Prolume, Ltd.||Apparatus and method for detecting and identifying infectious agents|
|US6649357||Apr 19, 2002||Nov 18, 2003||Prolume, Ltd.||Apparatus and method for detecting and identifying infectious agents|
|US6669927||Nov 1, 2001||Dec 30, 2003||3M Innovative Properties Company||Dental compositions|
|US6682721||Feb 13, 2001||Jan 27, 2004||Lg Household & Healthcare Ltd.||Patches for teeth whitening|
|US6689344||Sep 13, 2002||Feb 10, 2004||Lg Household & Healthcare Ltd.||Patches for teeth whitening|
|US6780401||May 27, 2003||Aug 24, 2004||Lg Household & Healthcare Ltd.||Patches for teeth whitening|
|US6803057||Dec 28, 2001||Oct 12, 2004||Virox Technologies Inc.||Hydrogen peroxide disinfectant with increased activity|
|US6884426||Dec 17, 2002||Apr 26, 2005||The Procter & Gamble Co.||Methods for whitening teeth|
|US6946142||Jun 20, 2002||Sep 20, 2005||Lg Household & Healthcare Ltd.||Multi-layer patches for teeth whitening|
|US6949240||May 23, 2002||Sep 27, 2005||The Procter & Gamble Company||Tooth whitening products|
|US7018622||Oct 24, 2002||Mar 28, 2006||The Procter & Gamble Company||Structures and compositions increasing the stability of peroxide actives|
|US7060253||Sep 20, 1996||Jun 13, 2006||Mundschenk David D||Topical formulations and delivery systems|
|US7094393||Aug 15, 2002||Aug 22, 2006||Britesmile Professional, Inc.||Tooth bleaching compositions|
|US7122199||Apr 6, 2005||Oct 17, 2006||The Procter & Gamble Company||Methods for whitening teeth|
|US7344656 *||Aug 6, 2004||Mar 18, 2008||Truox, Inc.||Storing a composition in an alcoholic gel|
|US7354604||Nov 17, 2003||Apr 8, 2008||Virox Technologies Inc.||Hydrogen peroxide disinfectant containing a cyclic carboxylic acid and/or aromatic alcohol|
|US7632523||Sep 11, 2006||Dec 15, 2009||Virox Technologies Inc.||Enhanced activity hydrogen peroxide disinfectant|
|US7785572||May 28, 2004||Aug 31, 2010||Lg Household And Health Care Ltd.||Method and device for teeth whitening using a dry type adhesive|
|US7803353||Mar 6, 2007||Sep 28, 2010||The Procter & Gamble Company||Oral care compositions having improved consumer aesthetics and taste|
|US7854349||Nov 25, 2003||Dec 21, 2010||The Gillette Company||Shave gel products|
|US7862802||Aug 10, 2004||Jan 4, 2011||Lg Household & Health Care Ltd.||Patches for teeth whitening|
|US8574555||Feb 1, 2007||Nov 5, 2013||Premier Dental Products Company||Stable one-part aqueous tooth whitening composition|
|US8580234||Oct 23, 2009||Nov 12, 2013||Kao Corporation||Method for removing solid product formed on surfaces of teeth|
|US8637085||Mar 21, 2012||Jan 28, 2014||Virox Technologies Inc.||Enhanced activity hydrogen peroxide disinfectant|
|US8647607||Apr 28, 2006||Feb 11, 2014||Lg Household & Health Care Ltd.||Patches for teeth whitening|
|US8652446||Nov 19, 2003||Feb 18, 2014||Lg Household & Healthcare Ltd.||Apparatus and method for whitening teeth|
|US8999400||Mar 2, 2012||Apr 7, 2015||Virox Technologies Inc.||Enhanced activity hydrogen peroxide disinfectant|
|US9233180||Oct 17, 2013||Jan 12, 2016||Virox Technologies Inc.||Hydrogen peroxide disinfectant containing a cyclic carboxylic acid and/or aromatic alcohol|
|US9554976||Jul 30, 2013||Jan 31, 2017||The Procter & Gamble Company||Tooth whitening product|
|US20020141951 *||Nov 1, 2001||Oct 3, 2002||R. Eric Montgomery||Tooth bleaching compositions|
|US20030059381 *||Oct 24, 2002||Mar 27, 2003||Goodhart Lesle Marie||Structures and compositions increasing the stability of peroxide actives|
|US20030180377 *||Feb 12, 2003||Sep 25, 2003||Ramirez Jose A.||Enhanced activity hydrogen peroxide disinfectant|
|US20040166085 *||Feb 21, 2003||Aug 26, 2004||Gurusamy Manivannan||Shave gel compositions|
|US20040166086 *||Nov 25, 2003||Aug 26, 2004||Gurusamy Manivannan||Shave gel products|
|US20040197270 *||Apr 1, 2003||Oct 7, 2004||Mundschenk David D.||Topical formulations and delivery systems|
|US20050032660 *||Aug 6, 2004||Feb 10, 2005||Martin Perry L.||Storing a composition in an alcoholic gel|
|US20050058719 *||Nov 17, 2003||Mar 17, 2005||Ramirez Jose A.||Hydrogen peroxide disinfectant containing a cyclic carboxylic acid and/or aromatic alcohol|
|US20050220725 *||Jan 30, 2004||Oct 6, 2005||Nathoo Salim A||Metal activated tooth whitening compositions|
|US20060193794 *||Apr 28, 2006||Aug 31, 2006||Ji-Young Kim||Patches for teeth whitening|
|US20060251591 *||Jul 13, 2006||Nov 9, 2006||Britesmile Professional, Inc.||Tooth bleaching compositions|
|US20070059380 *||Sep 11, 2006||Mar 15, 2007||Ramirez Jose A||Enhanced activity hydrogen peroxide disinfectant|
|US20070202059 *||Feb 1, 2007||Aug 30, 2007||Premier Dental Products Company||Stable one-part aqueous tooth whitening composition|
|US20070231278 *||Mar 6, 2007||Oct 4, 2007||The Procter & Gamble Company||Oral care compositions having improved consumer aesthetics and taste|
|US20080305182 *||Feb 8, 2008||Dec 11, 2008||Ramirez Jose A||Hydrogen peroxide disinfectant containing a cyclic carboxylic acid and/or aromatic alcohol|
|US20100003343 *||Sep 11, 2009||Jan 7, 2010||Ramirez Jose A||Enhanced activity hydrogen peroxide disinfectant|
|US20100330196 *||Sep 1, 2010||Dec 30, 2010||Ramirez Jose A||Enhanced activity hydrogen peroxide disinfectant|
|US20110223119 *||Oct 23, 2009||Sep 15, 2011||Kao Corporation||Method for removing solid product formed on surfaces of teeth|
|US20110281230 *||Jul 25, 2011||Nov 17, 2011||Biolase Technology, Inc.||Transparent dentifrice for use with electromagnetic radiation emitting toothbrush system|
|USRE42024||Dec 29, 2005||Jan 11, 2011||3M Innovative Properties Company||Dental compositions|
|USRE42126||Jun 30, 2000||Feb 8, 2011||The Procter & Gamble Company||Delivery system for oral care compositions comprising organosiloxane resins using a removable backing strip|
|WO2005013913A2 *||Aug 9, 2004||Feb 17, 2005||Materials Technology Laboratories, Inc.||Peroxygen containing particle in an alcohol containing gel|
|WO2005013913A3 *||Aug 9, 2004||Dec 15, 2005||Materials Technology Lab Inc||Peroxygen containing particle in an alcohol containing gel|
|U.S. Classification||424/53, 424/616|
|International Classification||A61K8/22, A61K8/90, A61K8/00, A61K33/40, A61K8/86, A61K8/34, A61Q11/00, A61K8/18|
|Cooperative Classification||A61K8/345, A61K8/22, A61Q11/00, A61K8/042, A61K8/90|
|European Classification||A61K8/34D, A61K8/22, A61Q11/00, A61K8/90, A61K8/04A|
|Aug 24, 1990||AS||Assignment|
Owner name: CHESEBROUGH-POND S USA CO., DIVISION OF CONOPCO, I
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:WILLIAMS, DAVID R.;RYLES, CHRISTINE W.;REEL/FRAME:005422/0291
Effective date: 19900706
|Nov 21, 1994||FPAY||Fee payment|
Year of fee payment: 4
|Nov 16, 1998||FPAY||Fee payment|
Year of fee payment: 8
|May 18, 1999||REMI||Maintenance fee reminder mailed|
|Apr 21, 2003||FPAY||Fee payment|
Year of fee payment: 12
|Nov 7, 2003||AS||Assignment|
Owner name: CHURCH & DWIGHT CO., INC., NEW JERSEY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CONOPCO, INC. DBA CHESEBROUGH POND S USA CO.;REEL/FRAME:014669/0304
Effective date: 20031020
|Nov 21, 2003||AS||Assignment|
Owner name: JPMORGAN CHASE BANK, AS ADMINISTRATIVE AGENT, TEXA
Free format text: SECURITY AGREEMENT;ASSIGNOR:CHURCH & DWIGHT CO., INC. (DELAWARE CORPORATION);REEL/FRAME:014146/0301
Effective date: 20031020